서지주요정보
(A) study on size-controlled $Pt_3Co$ intermetallic catalyst using potassium chloride substrates = 염화 칼륨 지지체를 이용한 $Pt_3Co$ 금속간화합물 촉매의 입자 크기 제어에 관한 연구
서명 / 저자 (A) study on size-controlled $Pt_3Co$ intermetallic catalyst using potassium chloride substrates = 염화 칼륨 지지체를 이용한 $Pt_3Co$ 금속간화합물 촉매의 입자 크기 제어에 관한 연구 / Hyo-Jong Kim.
발행사항 [대전 : 한국과학기술원, 2020].
Online Access 원문보기 원문인쇄

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등록번호

8035708

소장위치/청구기호

학술문화관(문화관)B1층 보존서고

MMS 20014

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리뷰정보

초록정보

The sluggish oxygen reduction reaction (ORR) at the cathode mainly increases overpotential of the polymer electrolyte membrane fuel cell (PEMFC). To improve ORR activity without increase of Pt usages, Pt-based catalysts have been extensively studied. Among them, Pt-based intermetallic catalysts have attracted attention with its enhancement in activity and stability. However, particle growth during high temperature heat treatment for ordered structure was major hurdle during synthesis. Here, we introduced potassium chloride (KCl) as a temporary substrate to synthesize $Pt_3Co$ intermetallic nanoparticles with keeping distances among the nanoparticles during the heat treatment. The size-controlled $Pt_3Co$ nanoparticles were sustained to 2.4 nm even with $Pt_3Co$ intermetallic phases. After all procedure, they were transported to carbon support with good dispersion. The prepared $Pt_3Co$/C catalysts showed 1.6-fold enhancement of mass activity and 6.3-fold enhancement of specific activity than commercial Pt/C. After 20k cycles of voltage cycling, the mass activity decreased only 0.8 % with extraordinary durability. Both intermetallic phases and the smaller particle sizes drew the synergy effect on the activity and stability. All the results revealed the possibilities of synthesis on KCl temporary substrate as well as development of $Pt_3Co$/C intermetallic catalysts.

고분자 전해질 연료전지 (polymer electrolyte membrane fuel cell, PEMFC)의 느린 산소 환원 반응 (oxygen reduction reaction, ORR)은 과전압의 주된 원인이다. 산소 환원 반응 속도를 향상시키기 위해 백금을 촉매로 사용하고 있으나, 가격 저감과 수명 향상을 위해 촉매의 활성과 안정성을 향상시키는 것이 필요하다. 그 방안으로 제시된 백금계 금속간 화합물 촉매는 우수한 성능과 내구성을 가지지만, 합금 나노 입자 제조 후 금속간 화합물로 상전이를 유도하는 열처리 과정에서 나노 입자의 크기가 성장하는 문제가 발생한다. 본 연구에서는 과량의 염화 칼륨을 임시 지지체로 이용, 입자간 거리를 제어하여 $Pt_3Co$ 합금 나노 입자의 금속간 화합물 형성을 위한 열처리를 진행함으로써, 열처리 과정에서 발생하는 나노 입자의 성장을 억제하였다. 이후 나노 입자를 탄소 담체에 분산시켜 $Pt_3Co$/C 촉매를 제조하였으며, 합성된 $Pt_3Co$ 금속간 화합물 입자의 크기는 2.4 nm 로 유지되었다. $Pt_3Co$/C 촉매는 상용 Pt/C 촉매 대비 질량 활성도는 1.6 배, 비 활성도는 6.3 배의 향상을 보여주었으며, 20,000 회의 전압 사이클 이후에도 초기 활성 대비, 단, 0.8 % 감소하는 우수한 내구성을 나타냈다. 즉, 염화칼륨 지지체를 활용한 열처리 합성법을 통해 촉매 입자 크기를 조절하여 $Pt_3Co$ 금속간화합물을 합성함으로써 산소 환원 반응에 대한 활성과 내구성을 향상시킬 수 있었다.

서지기타정보

서지기타정보
청구기호 {MMS 20014
형태사항 vi, 54 p. : 삽화 ; 30 cm
언어 영어
일반주기 저자명의 한글표기 : 김효종
지도교수의 영문표기 : EunAe Cho
지도교수의 한글표기 : 조은애
학위논문 학위논문(석사) - 한국과학기술원 : 신소재공학과,
서지주기 References : p. 49-52
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1 Several types offuel cells

1 (a) The scheme of polymer electrolyte membrane fuel cell (PEMFC) (b) the scheme of membrane electrode assembly (MEA) and (c) the equation ofreaction

The overpotential ofPEMFC and the ratio of cathode activation

The correlation between ORR activity and the oxygen ad/desorption energy ofPt alloy catalysts [1]

(a) Ni composition change ofPtxNiy catalysts duringelectrochemical activation (b) decrease of mass activity ofPtrNiy catalysts after 4,000 voltage cycles [42]

The example scheme ofPtsCo/CB synthesis using surfactant [29]

2 Literature survey about PtsCo or PtCo intermetallic catalysts

Overall procedure to synthesize PtsCo/C catalysts on KCl temporary substrate

TEMimages ofPt nanoparticle on KCl substrate

TEM images ofPtsCo/C synthesized using 10 g ofKCl

TEM images ofPtsCo/C synthesized using 20 g ofKCl

4 TEM images ofPtsCo/C synthesized using 40 g ofKCl

5 TEM images ofPtsCo/C synthesized using 80 g ofKCl

6 TEM images ofPtsCo/C synthesized using 160 g ofKCl

7 Nanoparticle size ofPtsCo with the variation ofKCl amount

XRD patterns ofPtsCo/C with the variation ofKCl amount

9 HR-TEM images ofPtsCo/C

1 Lattice parameter ofPtsCo from PDF #01-072-9179

Chemical composition ofPtsCo before transport to carbon substrate

Chemical composition ofPtsCo after transport to carbon substrate

10 (a) ORR activity ofPtrCo/Cin Oz-saturated 0.1M HCIO4 at a scan rate 20 mV/s, rotating speed 1600 rpm (b) Cyclic voltammetry (CV) ofPtrCo/C in Ar-saturated 0.1M HCIO4 at a scan rate 50 mV/s with the variation ofKCl amount

The comparison of(a) ORR activity and (b) CV curve of8 wt% and 16 wt% PtsCo/C catalysts

(a) Mass activity (A/mgpt), (b) ECSA (m2/gpt) and (c) specific activity (mA/cm2) ofPtrCo/C with the variation ofKCl amount versus commerical Pt/C

Current- voltage curve (IV curve) ofcommercial Pt/C and PtsCo/C tested on 5 cm2 MEA

15(a) ORR activity and (b) CV curve ofcommercial Pt/C after accelerated durability test (ADT)

14 (a) ORR activity and (b) CV curve ofPtsCo/C_on carbon after accelerated durability test (ADT)

16 (a) ORR activity and (b) CV curve ofPtsCo/C_om KCl after accelerated durability test (ADT)

(a) Mass activity (A/mgpt) and (b) ECSA (m2/gpi) ofPt/C and PtsCo/C after accelerated durability test (ADT)

18 TEM images ofPt/C synthesized using KCl (a) before and (a) after accelerated durability test (ADT)

19 TEM images ofPtrCo/C on carbon (a) before and (a) after accelerated durability test (ADT)

20 TEMimages ofPtrCo/C on KCl (a) before and (a) after accelerated durability test (ADT)

Chemical composition ofPtsCo/C_ on carbon and PtsCo/C_on KCl before and after accelerated durability test (ADT)

XPS results about(a) C1s,(b)o1s,(c)Pt 4f and (d) Co2p ofcommercial Pt/C

22 XPS results about(a)C1s,(b)01s,(c) Pt 4fand (d) Co2p ofPtsCo/C on carbon

XPS results about(a) C1s,(b)01s, (c)Pt4f, (d) Co2p,(e)K2p and (f)Cl2p ofPtsCo/C_on KCl

Relative area ratio ofC 1s peak of commercial Pt/C measured from XPS

6 Relative area ratio ofC 1s peak ofPtrCo/C on carbon measured from XPS

Relative area ratio ofC 1s peak ofPtsCo/C_on KCl measured from XPS

Relative area ratio ofPt 4f peak of commercial Pt/C measured from XPS

9 Relative area ratio ofPt4f peak ofPtrCo/C on carbon measured from XPS

10 Relative area ratio ofPt4fpeak ofPtsCo/C_ on KCl measured from XPS